Polyvinyl chloride-polysulfone resin



'8,755, filed February 2,719,139 Patented Sept. 27, 1955 IOLYVINYLCHLORIDE-POLYSULFONE RESIN COMPOSITIONS John E. Wicklatz, Bartlesville,Okla., assignor to Phillips Petroleum Company, a corporation of DelawareNo Drawing. Application November 18, 1952, Serial No. 321,267

12 Claims. (Cl. 260-455) This invention relates to new resinouscompositions of matter. In one aspect it relates to an improvedpolyvinyl chloride resin. In another aspect, it relates to a polyvinylchloride-containing resin having improved moldability. In anotheraspect, it relates to a method of increasing the moldability of apolyvinyl chloride resin. In another aspect, it relates to a method ofproviding a cheap additive to improve the moldability or plasticity of apolyvinyl chloride resin. In still another aspect, it relates to a newmixed resin.

Polyvinyl chloride resins are known and have been used in the art for avariety of purposes such as the production of molded articles, sheetmaterials, coatings and the like. Polyvinyl chloride resins are valuableparticularly on account of their chemical inertness. A pure polyvinylchloride resin, however, can be molded only with great difficulty and,therefore, requires the addition of relatively large amounts ofplasticizers such as dimethoxy diethyl phthalate, ethyl phthalyl ethylglycollate (Santicizer E-lS), dioctyl phthalate, and the like.Plasticizers of this type are of relatively low molecular weight andvolatilize readily, thus being lost on storage or handling. Some arereadily soluble in water and may be leached out when brought in contactwith water.

This invention solves the problem of moldability of polyvinyl chlorideresins by providing an additive which improves the moldability, does notvolatilize, and is not leached out by water.

According to this invention, there is provided a novel resin comprisinga major proportion of polyvinyl chloride and a minor proportion of aresin produced by the copolymerization of sulfur dioxide with anunsaturated organic compound.

The amount of unsaturated compound-sulfur dioxide resin added is in therange 5 to 50 weight per cent, preferably to weight per cent, based onthe total weight of the two resins. The unsaturated compound-sulfurdioxide resins utilized according to this invention are those resinsobtainable by the copolyme nation of sulfur dioxide and an unsaturatedcompound such as an openchain mono-olefin, a diolefin, an acetyleniccompound, an unsaturated aliphatic nitrile and similar compounds. Suchresins are producible by methods known in the art such as catalyticpolymerization of the organic compound together with the sulfur dioxidein the homogeneous solution or by the emulsion polymerization method, asset forth in Crouch and Cotten application, Serial No. 16, 1948, now U.S. Patent 2,645,631 (1953). Although a wide variety of unsaturatedorganic compounds can be used to produce the unsaturated organiccompound-sulfur dioxide resin, an especially satisfactory type ofunsaturated compound is an open-chain mono-olefin. The mono-olefin usedpreferably contains from 3 to 12 carbon atoms per molecule and morepreferably from 4 to 8 carbon atoms per molecule. The mono-olefins canbe used in the pure state or commercially available mixtures such asrefinery olefin cuts can be used. Examples of suitable olefins arel-butene, Z-butene, propylene, pentenes, hexenes, heptenes, octenes,decenes. Olefin-S02 resins are often referred to as polysulfone resins.

Polyvinyl chloride resins are well known in the art and are commerciallyavailable materials.

Further in accordance with this invention, polyvinyl chloride resins ofincreased moldability can be obtained by mixing a powdered polyvinylchloride resin with a powdered polysulfone resin in the desiredproportions, heating the mixture and forcing it into a mold. vAftermolding, the resin is cooled and recovered. The two powdered resins canbe ground together and the mixture obtained can be heated and molded aspreviously stated. Another method of preparing the resins according tothis invention comprises mixing a stabilized polyvinyl chloride latexwith a polysulfone latex, coagulating the mixed resin by the addition ofa suitable coagulating agent, recovering the coagulated mixture, washingthe mixture, and drying. The dried resin can be ground or pulverized andsubjected to injection molding or similar molding operations. Suitablecoagulating agents are methanol, sodium chloride, calcium chloride,magnesium sulfate and the like. The resin compositions of this inventioncan also be employed advantageously to form relatively thin films whichare useful in the packaging art, and the like.

It is also within the scope of this invention to add to the mixedpolysulfone-polyvinyl chloride resin known additives such as additionalplasticizers, coloring agents and thermal stabilization agents.

The mixed resins of this invention are readily moldable at lowertemperatures than are ordinarily used for polyvinyl chloride alone. Theresins obtained have improved color characteristics over the purepolyvinylchloride resins.

It is believed that the mixed resins produced according to thisinvention do not undergo chemical interaction during the mixing andmolding steps. However, this fact has not been definitely established.Nevertheless, the resins obtained have the highly satisfactoryproperties set forth herein and the term mixed resin in this specificatand in the claims is intended to cover the product ob. 'aed by mixingand molding regardless of whether chemical interaction of the componentsoccurs.

Example I A polysulfone resin was prepared using the following emulsionrecipe:

Parts by weight .Z-butone-cls 2-hu tone-trims The polymerization wasconducted for a period of seven hours at a temperature of F.

At the end of the reaction period the reactor was ope red and excesssulfur dioxide vented therefrom. Coagulation was effected with methanol;the resin was then rccovered by filtration, washed and dried in air atto F. for 16 hours.

Example II A series of compositions was made according to the teachingof the present invention using varying ratios of polyvinyl chloride andpolysulfone. The polysulfone was made according to the procedure ofExample I. The compositions so prepared were molded in an injectionmolding machine into discs 1.5 inches in diameter b 0.125 inch inthickness. The die cavities were provided with gates (openings to allowentrance of the resin into the die cavity) of .010 and .050 inch'inwidth. Resin compositions, molding conditions and appearance of themolded pieces are recorded below:

Pla sticizers used in runs G, H, K, L, M, O, and in the foregoing tablew the mixed resin at big ticizers used in runs B, D, and E.

Example IV ere found to be compatible with her concentrations than theplas- The hardness and plasticity of several resins prepared Com sitionsParts f wemfi, Molding Conditions Under Die Molding s?" T???" 01 vinylPolyaul- T 9 Seconds P y Pressure. Chloride l tone A Peenmoe 0t Molded gwe and Remarks Wouldnotinold. cisvir imeteiy one-e zhth badly Fullymolded pieces;

tilled through Fully molded peees; deep am Min color. Dieeevitlee comletel iiiiedthreushbot .01 end .060" rates.

with .010" gates proxiilled. Cavity with .0450" gets no textmatel two-tirds filled. ieeeshleokend deep amber in color. Die eevities eompletezg010" and .050" tee.

' Goon 151.

Example III Several mixed resins were prepared by adding to acommercially available polyvinyl chloride resin (Geon) difierentproportions of a polysulfone resin prepared as in accordance with thisinvention are shown in the followdescribed in Example I. Commerciallyavailable plasti- 36 Own i cizers were also added to the resins. Theproperties of the mixed resins, as compared with the properties ofpolyvinyl chloride resins containing commercial plasticizers are shownin the following table:

in; table:

SERIES I.UNPLABTIOIZED BLENDS Composition oi Resin Hnrd- PlasticityBlend ness (sq. in.)

Bus l. 3 7

S01 resin. 00/10 Goon ibl/l-butene R117 1.92

, 80; resin. 75/25 Goon ibi/i-bntene- 13.116 2.66

B01 resin. 60/60 Goon lblll-buteno- RilB 3.43

801 resin.

PHYSICAL PROPERTIES OF POLYVINYL OKLORIDE-POLYBULFONE BLENDB eon o ye mmRun 10;, sulione, Plastioiser, Parts aw Freeze Toughness Parts Parts100% BM Point Elen 20 DO 1, 900 2, 940 300 -22 530 Q) Do 1, 520 2,100250 -35 320 25 DO 1, 000 2, B60 296 -8 400 25 DO 1, 470 2, 640 200 10350 25130 1,100 2,140 275 -10 310 50 E-l 1, 700 3, 300 336 -6 01B 00 E-l1, 500 3,060 305 -10 590 50 E-lb 1, W 2, 870 365 16 58 20 E-1 1, 900 3,230 255 1.1 425 30 E'l 1, 600 3, 250 320 --9 560 20 15-1 1,440 2, 780see -14 530 25 E-l 1, 400 2, 800 340 -15 500 30 E4 1, 410 2,000 306 u420 25 E 1, 000 3,16 300 -20 090 25 1 1-15, 1,260 2,080 300 48 4 E10,1OTEO- 2,060 3,400 290 8 550 0 3-15, 10 TE 1, 320 2, 84 37 "16 530 one:

TOF-trlootyl hosphete. DOP-Di- 2 et ylhexylz phthslete. E-lb-eth phthellet {I lyeonete. Methoxi-(Qmet one by )-phthalste. TEO-trieth leitre te.Tonghneset.-ibs. at work to break specimen 011.0 sq. in. cross-sections]Dunn-none:

i. All Goon-l0i-polysulione blends require less Pull roi- 1007leloggetion thin own mi. 'riiis mailers On I.

thst the plastloizer is m m eiieetive in the (lean-i0 polysulione 2. Insome instances the percent elongation is improved. 3. Gehman ireezepoint oizgeneinlly lowered. 4. Toughness remains I Corn iosltlon o1Rosin Hard- Plasticity l Blend Plestlclzer ms (w m) 100/0 Geonlblll-butene- SnntlclzerB' R105 3.65

SO1resln.

/10 Goon llil/l-hutentr do E90 4.72

EiOrresln.

75/26 Goo. lblll-butene' d0 R82 5.

SO: resin.

150/50 Goon llilll-buteno- .....do R02 0.15

801 rosin.

100/0 Geon151/1-butene- Santlcize:E-1li"..... B2 1.27

SO; rosin.

90/10 Goon lblll-butuno- .....do E17 0.28

SOrrosln.

75/25 Goon lbl/l-butenedo R68 5.72

O: rosin.

50/50 Goon llilll-butono- .....do E41 0.30

501 resin.

100/0 Geon l61/1-butene- Floxol DOP"'... R15 3.00

301 tOSlD.

90/10 Goon 161/1-butene- R44 4.60

SOzresln.

75/25 Oeon lblll-butone- R60 5.48

1501 resln.

50/50 Goon lblll-butene' R11 6.48

SO: resin.

SERIES IIL-PLASIICIZED BLENDS (GEON 151/PLASTICIZER-75/25) 100/0 Geonlfilll-butene- Santlclzer E-15 R48 2.92

90/10 Geon lolll-butene- .-...do E29 4.32

SOyresln.

75/25 Geon151/1-buteno .....do E28 5.00

zresln.

50/50 Geon lbl/l-butene- .....do R101 4.63

SOirosln.

oand p-'loluene ethyl 'sulionamldes.

"Ethyl phtlialyl ethyl glycollate.

"'Dl-(Z-ethylhexyl) phtlialate.

The plasticity was determined in the following manner: A disc one inchin diameter and with a thickness of 0.60:0.005 inch was placed betweentwo silver foil squares inches on a side). This "sandwich was preheatedfor exactly one minute at 255 F. and then 8000 p. s. i. pressure wasexerted on the disc for exactly one minute. The flattened disc wasquickly removed and quenched in cold water. After drying, an outline ofthe flattened disc was traced on graph paper. An outline of the originaldisc was also made prior to the above treatment. The ditference betweenthe area of the flattened disc and that of the original is taken as ameasure of the plasticity.

The values in the column entitled Hardness" are Rockwell hardnessnumbers.

The data in the foregoing table show that resins having satisfactoryhardness and plasticity, in addition to improved molding properties, areproduced in accordance with this invention.

Variation and modification are possible within the scope of thedisclosure and claims to this invention, the essence of which is that apolyvinyl chloride resin of improved moldability is obtained by addingto said resin a resin produced by the copolymerization of sulfur dioxidewith an unsaturated organic compound; and that a novel resin and a novelmethod of producing the same are provided.

I claim:

1. An improved resinous composition of matter comprising a majorproportion of a polyvinyl chloride resin and a minor proportion of aresin produced by the copolymerization of sulfur dioxide with anunsaturated organic compound.

2. A polyvinyl chloride resin having improved moldability, said resincomprising a polyvinyl chloride resin and an olefin-sulfur dioxideresin, the amount of said olefin-sulfur dioxide resin being in the range5 to weight per cent, based on the total weight of said resins.

3. A mixed resinous composition comprising a polyvinyl chloride resinand an olefin-sulfur dioxide resin, said latter resin constituting from10 to 25 weight per cent of the total weight of said polyvinyl chlorideresin and said olefin-sulfur dioxide resin.

4. A resin in accordance with claim 3 in which the olefin-sulfur dioxideresin is a l-butene-sulfur dioxide resin.

5. A resinous composition according to claim 3 in which saidolefin-sulfur dioxide resin is a propylene-sulfur dioxide resin.

6. A resinous composition in accordance with claim 3 in which saidolefin-sulfur dioxide resin is a pentenesulfur dioxide resin.

7. A resinous composition in accordance with claim 3 in which saidolefin-sulfur dioxide resin is a hexene-sulfur dioxide resin.

8. A resinous composition according to claim 3 in which saidolefin-sulfur dioxide resin is a heptene-sulfur dioxide resin.

9. A method for molding a polyvinyl chloride resin which comprisesadding to said resin a minor proportion of a resin produced by thecopolymerization of sulfur dioxide with an unsaturated organic compound;subjecting the mixture so obtained to heating and molding; andrecovering a molded resinous mass.

10. A method of molding a polyvinyl chloride resin which comprisesadding to said resin a minor proportion of an olefin-sulfur dioxideresin; subjecting the mixture to molding; and recovering a moldedresinous article.

11. A process for producing a molded resinous article which comprisesmixing a powdered polyvinyl chloride resin with from 5 to 50 weight percent of an olefinsulfur dioxide resin, based on the total weight of thetwo resins; subjecting the mixture to molding; and recovering a moldedarticle.

12. A process for molding a polyvinyl chloride resin which comprisesmixing with a stabilized polyvinyl chloride latex a stabilizedolefin-sulfur dioxide latex, the latices being mixed in such proportionsthat the mixture contains from 10 to 25 weight per cent of olefin-sulfurdioxide copolymer based on the weight of total copolymer present,subjecting the mixed latex to coagulation, removing coagulated material,washing and drying said coagulated material, grinding the dried materialto a powder. sub jecting said powder to molding, and recovering a moldedresin.

References Cited in the file of this patent Great Britain Oct. 31. 1951

1. AN IMPROVED RESINOUS COMPOSITION OF MATTER COMPRISING A MAJORPROPORTION OF A POLYVINYL CHLORIDE RESIN AND A MINOR PROPORTION OF ARESIN PRODUCED BY THE COPOLYMERIZATION OF SULFUR DIOXIDE WITH ANUNSATURATED ORGANIC COMPOUND.